EP1298118A2 - Prozess für die Herstellung von 5-Arylpentanolen - Google Patents
Prozess für die Herstellung von 5-Arylpentanolen Download PDFInfo
- Publication number
- EP1298118A2 EP1298118A2 EP20020021724 EP02021724A EP1298118A2 EP 1298118 A2 EP1298118 A2 EP 1298118A2 EP 20020021724 EP20020021724 EP 20020021724 EP 02021724 A EP02021724 A EP 02021724A EP 1298118 A2 EP1298118 A2 EP 1298118A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- group
- carbon atoms
- catalyst
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
Definitions
- the present invention relates to a process for producing 5-arylpentanols that are useful as synthetic intermediates of perfume, medicaments, agricultural chemicals and the like from pyran compounds.
- An object of the present invention is to provide a process for producing a 5-arylpentanol in a high yield with little amount of by-products.
- Another object of the invention is to provide a process for producing a 5-arylpentanol which does not bring about a problem with regard to corrosion of process equipment and is industrially satisfactory.
- the present inventors have found, after intensive researches, that the aimed product can be obtained in a high yield and industrially satisfactorily while suppressing production of by-products without using a special corrosion-resistant equipment by effecting hydrogenolysis in the presence of a supported catalyst of two or more elements selected from the noble metals in Group VIII in the periodic table and/or an acidic-type palladium-supporting catalyst, and have completed the invention.
- R 1 is preferably an aryl group having in total 6 to 12 carbon atoms which may be substituted with one or two or more of alkyl or alkoxy groups each having 1 to 6 carbon atoms.
- the aryl group includes phenyl group and naphthyl group, and is preferably phenyl group.
- R 1 is particularly preferably phenyl, or o-, m- or p-tolyl, and most preferably phenyl.
- R 2 is preferably a hydrogen atom or an alkyl or alkylidene group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl group or methylene group, and most preferably a hydrogen atom or methyl group.
- R 3 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or methyl group.
- Examples of the pyran compounds include 6-phenyl-4-methyl-5,6-dihydro-2H-pyran, 6-phenyl-2,4-dimethyl-5,6-dihydro-2H-pyran, 6-p-tolyl-4-methyl-5,6-dihydro-2H-pyran, 2-phenyl-4-methylenetetrahydro-2H-pyran, and 2-phenyl-4-methyl-5,6-dihydro-2H-pyran.
- One of the preferred embodiments of the present invention is a process for producing a 5-arylpentanol of formula (2a): wherein,
- R 1 and R 3 are the same as those described for R 1 and R 3 in formula (1).
- R 2a is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or methyl group.
- the noble metals include palladium, platinum, rhodium and ruthenium.
- Carriers for the noble metals include carbon, alumina, silica gel, barium sulfate, zeolite and calcium carbonate.
- the catalyst may be two or more noble metals supported on one kind of carrier, or a mixture of two or more kinds of carriers each carrying one kind of noble metal.
- the amount of each noble metal supported on a carrier is preferably 0.1 to 10% by weight, and more preferably 0.2 to 8% by weight of the catalyst.
- Total amount of two or more noble metals supported on carrier(s) is preferably 1 to 20% by weight, more preferably 2 to 10% by weight of the catalyst.
- catalysts can be obtained by a well known method, for example by an impregnation supporting method ( "Catalyst Preparation Chemistry” edited by Atsumu Ozaki, published by Kodansha) in which a carrier is impregnated with a metal and the resulting carrier is reduced with hydrogen at a higher temperature.
- an impregnation supporting method "Catalyst Preparation Chemistry” edited by Atsumu Ozaki, published by Kodansha) in which a carrier is impregnated with a metal and the resulting carrier is reduced with hydrogen at a higher temperature.
- commercial products may be used as they are. Examples of such commercial products include Palladium-Platinum-Carbon powder, Palladium-Carbon Powder, Platinum-Carbon Powder, and Ruthenium-Carbon Powder each manufactured by N. E. Chemcat Corporation.
- the acid type palladium-supporting catalyst used in the present invention means such a solid palladium catalyst in which palladium is supported on at least one carrier selected from alumina, silica gel, barium sulfate, zeolite and calcium carbonate and which shows a pH of less than 7, preferably 2 to 6, particularly preferably 3 to 5.5 when it is dispersed in water.
- a carrier selected from alumina, silica gel, barium sulfate, zeolite and calcium carbonate
- the resulting water has a pH of less than 7, preferably 2 to 6, particularly preferably 3 to 5.5. If the pH of the catalyst is not less than 7, production rate of a 5-arylpentanol significantly decreases.
- the amount of palladium in the catalyst is preferably 0.5 to 10% by weight, particularly 2 to 10% by weight of the catalyst.
- Such catalysts can be obtained by a well known method, for example by impregnating a carrier with a metal according to an impregnation supporting method ( "Catalyst Preparation Chemistry” edited by Atsumu Ozaki, published by Kodansha), and reducing the resulting carrier with hydrogen at a higher temperature.
- commercially available catalysts may be used.
- those having a pH in the above-mentioned range may be used.
- the amount of the catalyst to be used in the invention is usually in a range of 0.01 to 5% by weight, preferably in a range of 0.05 to 5% by weight based on the pyran compounds although it varies depending on the amount of the metals contained in the catalyst; use of too little amount of the catalyst results in a low reaction rate while use of too much amount of the catalyst results in much production of by-products such as hydrocarbons and excessive reaction products wherein the benzene ring of a 5-aryl pentanol is hydrogenated and thus is not economical.
- the catalyst carrying two or more elements selected from the noble metals in Group VIII in the periodic table is used, it is used in an amount of 0.01 to 2% by weight, preferably 0.05 to 1% by weight based on the pyran compounds. Either of the two kinds of the catalysts can be re-used.
- the reaction in the present invention may be carried out using a solvent.
- Alcohol solvents are preferred as the solvent and examples thereof include methanol, ethanol, 1-propanol and 2-propanl. These solvents may be used alone or as a mixture of two or more thereof.
- the amount of the solvent used in the reaction is preferably not more than 60% by weight based on the pyran compound. Alternatively, solvents may not be used.
- the reaction may be conducted at a constant temperature. However, it is preferable to conduct the reaction at a relatively lower temperature in the early stage of reaction and then increase the temperature at the later stage of reaction in order to suppress production of by-products and to increase the production rate of 5-arylpentanols.
- the later stage of reaction begins preferably from the time when conversion of the raw material, pyran compounds, reaches about 60 to 95%, particularly about 80 to 90%, which time usually corresponds to about 1 to 4 hours after commencement of the reaction although such time varies depending on the reaction temperature and the like.
- the reaction temperature in the later stage of reaction is preferably higher than that in the early stage of reaction.
- the temperature is increased with time at a rate preferably in a range of from 3 to 20°C per minute.
- Hydrogenolysis of the pyran compounds is effected at about 30 to 300°C, preferably at about 40 to 200°C.
- the reaction is desirably conducted at about 40 to 100°C, preferably 50 to 80 °C at the early stage of reaction. Thereafter, in the later stage of reaction, the reaction temperature is increased to a temperature higher than that in the early stage of reaction by about 30 to 260°C to enhance the production rate of 5-arylpentanols.
- the temperature in the later stage of reaction is preferably in a range of from about 120 to 180°C.
- Hydrogen pressure during reaction is in a range of 0.2 to 10MPaG, preferably 0.5 to 5MPaG; too lower hydrogen pressure results in insufficient production rate of 5-arylpentanols.
- reaction mixture was filtered to remove the catalyst and was analyzed by gas chromatography. As the result, the yield of 5-phenyl-3-methylpentanol was 93.4%.
- the reaction product contained 1.3% of hydrocarbons and 2.1% of excessive reaction products.
- reaction temperature was raised to 150°C in 19 minutes and reaction was conducted for additional 5 hours.
- reaction mixture was filtered to remove the catalyst and was analyzed by gas chromatography. As the result, the yield of 5-phenyl-3-methylpentanol was 93.0%.
- the reaction product contained 1.8% of hydrocarbons and 2.1% of excessive reaction products.
- reaction mixture was filtered to remove the catalyst and was analyzed by gas chromatography. As the result, the yield of 5-phenyl-3-methylpentanol was 92.0%.
- the reaction product contained 1.9% of hydrocarbons and 4.1% of excessive reaction products.
- reaction mixture was filtered to remove the catalyst and was analyzed by gas chromatography. As the result, the yield of 5-phenyl-3-methylpentanol was 93.1%.
- the reaction product contained 0.8% of hydrocarbons and 3.8% of excessive reaction products.
- 5-arylpentanol can be prepared in a high yield while suppressing production of hydrocarbons and without causing a problem with regard to corrosion of process equipment.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001296249 | 2001-09-27 | ||
JP2001296249 | 2001-09-27 | ||
JP2002169630A JP3881288B2 (ja) | 2001-09-27 | 2002-06-11 | 5−アリールペンタノールの製造法 |
JP2002169630 | 2002-06-11 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1298118A2 true EP1298118A2 (de) | 2003-04-02 |
EP1298118A3 EP1298118A3 (de) | 2003-07-16 |
EP1298118B1 EP1298118B1 (de) | 2008-02-13 |
Family
ID=26623052
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20020021724 Expired - Lifetime EP1298118B1 (de) | 2001-09-27 | 2002-09-25 | Prozess für die Herstellung von 5-Arylpentanolen |
Country Status (5)
Country | Link |
---|---|
US (1) | US6600079B2 (de) |
EP (1) | EP1298118B1 (de) |
JP (1) | JP3881288B2 (de) |
DE (1) | DE60224968T2 (de) |
ES (1) | ES2296860T3 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020144307A1 (de) * | 2019-01-11 | 2020-07-16 | Basf Se | Herstellung von 5-aryl-pentanolen |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104876800A (zh) * | 2015-04-03 | 2015-09-02 | 江苏绿源精细化工有限公司 | 一种苯乐戊醇的制备工艺 |
CN105924332B (zh) * | 2016-05-06 | 2020-06-09 | 山东新和成药业有限公司 | 一种3-甲基-5-苯基-戊醇的制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH655932A5 (en) * | 1983-02-24 | 1986-05-30 | Firmenich & Cie | Pyran derivatives, process for their preparation and their use for the preparation of aliphatic alcohols |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8800009A (nl) * | 1988-01-05 | 1989-08-01 | Naarden International Nv | Werkwijze voor de bereiding van dihydro-pyranen. |
US5219836A (en) * | 1992-07-27 | 1993-06-15 | Firmenich Sa | Use of tetrahydro-4-methyl-2-phenyl-2H-pyran as perfuming ingredient |
ES2241019T3 (es) * | 1996-10-03 | 2005-10-16 | Kao Corporation | Procedimiento para la preparacion de compuesto de dihidropirano. |
-
2002
- 2002-06-11 JP JP2002169630A patent/JP3881288B2/ja not_active Expired - Fee Related
- 2002-09-25 EP EP20020021724 patent/EP1298118B1/de not_active Expired - Lifetime
- 2002-09-25 ES ES02021724T patent/ES2296860T3/es not_active Expired - Lifetime
- 2002-09-25 DE DE2002624968 patent/DE60224968T2/de not_active Expired - Lifetime
- 2002-09-26 US US10/254,661 patent/US6600079B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH655932A5 (en) * | 1983-02-24 | 1986-05-30 | Firmenich & Cie | Pyran derivatives, process for their preparation and their use for the preparation of aliphatic alcohols |
Non-Patent Citations (1)
Title |
---|
R.H. BAKER ET.AL.: "THE CLEAVAGE OF BENZYL ETHERS WITH HYDROGEN" J. AM. CHEM. SOC., vol. 70, 1948, pages 1490-1492, XP002241175 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020144307A1 (de) * | 2019-01-11 | 2020-07-16 | Basf Se | Herstellung von 5-aryl-pentanolen |
CN113260603A (zh) * | 2019-01-11 | 2021-08-13 | 巴斯夫欧洲公司 | 5-芳基戊醇的制备 |
US11365168B2 (en) | 2019-01-11 | 2022-06-21 | Basf Se | Preparation of 5-aryl-pentanols |
CN113260603B (zh) * | 2019-01-11 | 2023-12-01 | 巴斯夫欧洲公司 | 5-芳基戊醇的制备 |
Also Published As
Publication number | Publication date |
---|---|
DE60224968T2 (de) | 2009-02-12 |
EP1298118A3 (de) | 2003-07-16 |
EP1298118B1 (de) | 2008-02-13 |
US6600079B2 (en) | 2003-07-29 |
US20030060667A1 (en) | 2003-03-27 |
ES2296860T3 (es) | 2008-05-01 |
DE60224968D1 (de) | 2008-03-27 |
JP3881288B2 (ja) | 2007-02-14 |
JP2003171323A (ja) | 2003-06-20 |
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